本研究先利用Grignard metathesis合成出2種單聚合物(PPDOT, P3HT) 和3種不同比例的共聚合物(PPDOT-co-P3HT=1:1, PPDOT-co-P3HT=3:1, PPDOT-co-P3HT=1:3)。
PDOT和3HT兩者都是富有電子基的單體，因PDOT比3HT對材料造成推效應的影響更大，因此會使共軛長度變長，導致HOMO能階降低，因而有效降低高分子的能隙。這些高分子能隙的範圍為1.908∼1.922 eV。這些材料有理想的吸收性質，因而被選用作為有機太陽能電池。
研究中，以TGA、DSC、XRD、GPC、NMR、UV、PL和AC-2作為量測，並針對其高分子作熱穩定性、結晶度、結構與光電性質上的分析與探討。從XRD中，了解到材料主鏈排列的結晶性還不錯，因而能增加噻吩環的吸光。由UV中看出红外光的吸收區域增加，有利於ISC提升，但也造成HOMO降低，盡而使VOC降低。但對於整體元件效率來說，ISC的提升遠大於VOC的降低，因此效率還是上升。但在PL中，放光的強度很大，會造成元件產生淬息，使其效率降低。
高分子材料經由UV-VIS與AC-2，了解到HOMO-LUMO能階匹配的關係，並與PCBM混合作為有機太陽能電池的主動層。從元件效率說明，因效率都不高，而為短路現象。其原因為 (1)能階上不能匹配 (2)PPDOT的溶解度不太好，因此成膜不易均勻。改善方法，找出較佳的溶劑溶解，增加其溶解度。

In this study, two kinds of homopolymers (PPDOT, and P3HT), and three different proportions of copolymers (PPDOT-co-P3HT=1:1, PPDOT-co-P3HT=3:1, and PPDOT-co-P3HT=1:3) have been synthesized successfully by Grignard metathesis.
PDOT and 3HT, which are both of monomers, are electron-donating. Due to the fact that PDOT was caused larger than 3HT by pushing effect, it can change the conjugation length to be much longer, resulting in lower energy level of HOMO, and thus reduce energy gap of high molecular. These polymers possess optical bandgaps in the range of 1.908 to 1.922 eV. The desirable absorption attributes of these materials make them to be the excellent candidates for use in organic solar cells.
In this study, the analysis and discussion of these polymers were measured by TGA, DSC, XRD, GPC, NMR, UV, PL, and AC-2 for thermal stability, crystallinity, structure and optical properties. From the XRD, materials of main chain ordered are well crystalline, which can increase the absorption of thiophene ring. By UV, we could find absorption region of infrared light increase that is beneficial to enhance ISC, but led to lower HOMO, and thus reduced VOC. However, the overall device power conversion efficiencies indicate that increasing ISC is much greater than decreasing VOC. Hence, power conversion efficiency increased. However, in PL, intensity of the emission is large, and it will cause components to quenching that lead to reduce its efficiency.
We knew HOMO-LUMO energy level matching relations of polymer materials which were mixed with PCBM as the active layer of organic solar cells by UV-VIS and AC-2. From the instructions of device power conversion efficiency, because efficiency is not high, it causes the short circuit. The reason is (1) energy level can not match (2) the solubility of PPDOT is not very good, hence the film is not easy even. The way to improve is to identify a better solvent to increase its solubility.

摘 要 III
Abstract V
誌謝 VII
目 錄 頁次 VIII
圖目錄 XII
表目錄 XVI
壹、緒論 1
1-1、有機共軛高分子 1
1-2、導電高分子的導電機制 4
1-2-1、能帶結構 4
1-2-2、極子(polaron)、雙偏極子(bipolaron)和孤立子(soliton) 9
1-3、導電高分子的應用 12
1-3-1、有機太陽能電池 12
1-3-2、有機電激發光二極體 13
貳、低能隙導電高分子的介紹 15
2-1、低能隙導電高分子的發展歷史 15
2-2、低能隙導電高分子的種類 15
2-3、聚噻吩系統 18
2-3-1、聚噻吩高分子能隙的調變〔26〕〔27〕 18
2-3-2、聚噻吩低能隙導電高分子的種類〔28〕 19
2-3-3、聚噻吩高分子的推拉效應 20
2-4、薄膜太陽能電池工作原理及功率轉換效率 21
2-4-1、太陽能電池的轉移機制 21
2-4-2、太陽能電池的光電轉換原理 22
2-4-2-1、光源能量吸收，產生激子(Exciton)，如圖2-4-2-1。 22
2-4-2-2、激發態分子擴散漂移(Drift)，如圖2-4-2-2。 23
2-4-2-3、電荷轉移，激子分離，如圖2-4-2-3。 23
2-4-2-4、電荷收集，如圖2-4-2-4。 23
2-4-3、太陽能電池的功率轉換效率 26
2-5、研究動機 28
參、實驗部份 29
3-1、實驗藥品 29
3-2、合成步驟 30
3-2-1、2,5-Dibromo-3-hexylthiophene合成 30
3-2-2、6,8-Dibromo-3,3-dibutyl-3,4-dihydro-2H-thieno [3,4-b]-[1,4]dioxepine.合成 31
3-2-3、 Poly(3,3-dibutyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)(PProDOT-Bu2).的格林納聚合反應 32
3-2-4、ProDOT-Bu2-Br2-co-3HT-Br2(1:1)的格林納聚合反應 33
3-2-5、ProDOT-Bu2-Br2-co-3HT-Br2(1:3)的格林納聚合反應 34
3-2-6、ProDOT-Bu2-Br2-co-3HT-Br2(3:1)的格林納聚合反應 35
3-3、儀器分析與樣品製備 44
3-3-1、熱重分析儀(TGA) 44
3-3-2、熱示差掃描卡量計(Differential Scanning Calorimeter, DSC) 44
3-3-3、粉末X-ray繞射儀（powder X-ray diffractmeter, XRD） 44
3-3-4、核磁共振光譜儀(NMR) 45
3-3-5、膠體滲透層析儀(GPC) 45
3-3-6、紫外與可見光光譜儀（UV-Vis Spectroeter） 46
3-3-7、螢光光譜儀(PL Spectroeter) 47
3-3-8、光電子光譜分析儀(Photo-electron spectroscopy in air，簡稱PESA) 48
3-3-9、陽光譜模擬量測系統（solar simulator system） 48
肆、結果與討論 50
4-1、高分子的熱性質與排列性 50
4-1-1、熱重分析(TGA) 50
4-1-2、微分示差卡瞄計(DSC) 51
4-2、高分子的結構性質 52
4-2-1、粉末X-ray繞射儀（XRD） 52
4-2-2、核磁共振光譜儀(NMR) 56
4-2-3、膠體滲透層析儀(GPC) 57
4-2-4、高分子的光學與電學性質 63
4-2-4-1、紫外與可見光光譜儀（UV-Vis Spectroeter） 63
4-2-4-2、螢光光譜儀(PL Spectroeter) 65
4-2-4-3、光電子光譜分析儀(PESA) 67
4-3、元件 71
伍、結論 73
陸、參考文獻 75

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